3-phenyl-5-(3,4,4-trifluoro-3-butenylthio)1,2,4-thiadiazole



United States Patent 3,513,1723-PHENYL-5-(3,4,4-TRIFLUOR0-3-BUTENYLTHIO) 1,2,4-THIADIAZOLE Mervin E.Brokke, Richmond, Calif., assignor to Staufier Chemical Company, NewYork, N.Y., a corporation of Delaware No Drawing. Filed Sept. 27, 1965,Ser. No. 490,664 Int. Cl. C07d 91/60 US. Cl. 260-302 1 Claim ABSTRACT OFTHE DISCLOSURE Certain trifluorobutenyl compounds of the formula CF=CFCH CH R wherein R is a member selected from the group consisting ofchlorothiophenyl, thio-3,4,4-trifluoro-3-butenyl, 2-thio-4,4,6-tri-methyldihydropyrimidyl, 2 thiobenzoxazoyl,2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S-(3,4,4-trifluoro 3butenyl)-ethylene-bis(dithiocarbamoyl), thiobenzyl, thionaphthyl,phthalimido, dithio-3,4,4-trifluoro-3- butenyl, thiopyridyl,N-thiazolidyl dione, and 5-thio-3- phenyl-l,2,4-thiadiazolyl, useful asnematocides.

This invention relates to certain new and novel chemical compounds andto the utility of said compounds as effective nematocides. Morespecifically, this invention relates to compounds of the general formulawherein R is a member selected from the group consisting ofchlorothiophenyl, thio-3,4,4-trifiuoro-3-butenyl, 2-thio-4,4,6-trimethyldihydropyrimidyl, 2 thiobenzoxazolyl, 2-thiobenzothiazolyl, 2-thio-4-alkylthiazolyl, S (3,4,4 trifluoro 3butenyl)-ethylenebis(dithiocarbamoyl), thiobenzyl, thionaphthyl,phthalimido, dithio-3,4,4-trifluoro- 3-butenyl, thiopyridyl,N-thiazolidyl dione, and 5-thio-3- phenyl-1,2,4-thiadiazolyl.

The compounds herein contemplated can be prepared by various methods.One such general method of preparing the compound with bonding by meansof a thio group is the condensation of the appropriate thiol (RfiSI-l)and 3,4,4-trifluoro-3-butenyl bromide, usually in the presence of anorganic base, such as triethylamine. Similarly, compounds whereinbonding is through a heterocyclic nitrogen condensation is accomplishedusing the appropriate sodium or potassium salt of the heterocyclicnitrogen containing compound and 3,4,4-trifluoro-3-butenyl bromide. Thereactions proceed readily in the liquid phase. The employment of aninert organic solvent is also useful, facilitating processing as well asagitation of the reactants. Temperatures that permit operation in theliquid phase and which are between room temperature and refluxtemperature of the solvent, if one is used, are employed. Preferably thereaction mixture is refluxed, usually at an elevated temperature.

It has been found that the compounds of the present invention areparticularly eflective as nematocides. They are effective in the controlof nematodes when applied to a nematodal habitat.

The compounds of the present invention may be prepared in accordancewith the following illustrative examples.

EXAMPLE 1 Preparation of p-chlorophenyl 3,4,4-trifluoro- S-butenylsulfide In 200 ml. methanol was dissolved 14.4 g. of plchlorothiophenol.To this solution was added 25 g. of 25 percent sodium methoxide followedby 18.9 g. of 3,4,4-tri- 3 ,5 l 3 ,1 72 Patented May 19, 1970 "iceEXAMPLE 2 Preparation of bis( 3,4,4-trifluoro-3-butenyl) ethylene-bisdithiocarbamate) Ethylene diamine (0.2 mole) and triethylamine (0.2mole) were dissolved in ml. of dioxane. Carbon disulfide (0.2 mole) wasadded dropwise with stirring at 1 020 C.; stirred at room temperaturefor 15 minutes after addition was completed, then heated to 40 C. for 15minutes. To the reaction mixture was added 0.15 mole (28.4 g.) of3,4,4-trifluoro-3-butenyl bromide. This was heated to 60 C. for 2 hours.The reaction mixture was poured into water and extracted with benzene.The benzene solution was subsequently washed with Water, dried overanhydrous calcium chloride and finally the benzene removed in vacuo.There was obtained 77.4 g. of the title compound, 11 1.5292.

EXAMPLE 3 Preparation of 3-phenyl-5- 3,4,4-trifiuoro-3-butenylthia)-1,2,4-thiadiazole 3-phenyl-l,2,4-thiadiazole thiol-S, 6.6g., were mixed with 9.5 g. of 3,4,4-trifiuoro-3-butenyl bromide in cc.of dioxane as solvent with 10.1 g. of triethylamine as the catalyst. Thereaction mixture was refluxed for 2 /2 hours. Isolation of the titlecompound was in the same manner as in Example 2. There was obtained 8.8g. of a dark oil, 21 1.5687.

EXAMPLE 4 Preparation of N-(3,4,4-trifluoro-3-butenyl)2,4-thiazolidenedione In 100 ml. of methanol there was dissolved 11.7 g.of 2,4-thiazolidenedione. This was treated with 0.1 mole of sodiummethoxide in methanol. To this solution was added 18.9 g. of3,4,4-trifluoro-3-butenyl bromide. The resulting mixture was refluxed 2hours. The solvent was then evaporated and the residue was taken up inbenzene. The benzene solution was Washed with Water, dried overanhydrous calcium chloride, and the solvent evaporated. There wasobtained 7.2 g. of the title compound, 11 1.4678. Analysis of theinfrared spectrum supported the proposed structure.

As previously mentioned, the herein described novel compositionsproduced in the above described manner are biologically active compoundswhich are useful and valuable in the control of various organisms. Thecompounds of the invention were tested as nematocides in the followingmanner.

Nematocia'e evaluation test-This test determines a candidates action onroot-knot nematodes (Meloidogyne, sp.) in soil. One-pound portions ofsoil infested with rootknot nematodes were placed in quart jars. Thechemical to be tested was pipetted into the nematode-infested soil atvarious dilutions of from 55 to 1 part per million (p.p.m.) or untilactivity was lost. After mixing the candidate compound into the soil,the soil was sealed for 48 hours. The treated soil was then placed inpaper containers and allowed to stand in a greenhouse one week forairing. At the end of this time a tomato plant was transplanted into thesoil. The root-knot nematodes attack the tomato plant roots if theysurvived the chemical treatment, and cause swelling or knots on theroots. Four weeks after treatment the plant was removed from the soiland the roots inspected. The lowest concentration which preventednematode development was recorded.

The following table is a listing of the compounds prepared according tothe aforedescribed procedures. Column II is the results obtained fromthe nematocide evaluation test. The values given in Column II areconcentrations (p.p.m.) which allowed no nematode development.

TAB LE Column I Column II Nematode control Compound 7111 (p.p.m.)

p-Chlorophenyl 3,4,4-trifiuoro-3-butenyl sulfide 1. 5360 50 Bis(3,4,4-trifiuoro-3-but enyl) sulfide 1. 4087 2.2-(3,4,4-tritluoro-3-butenylthio)-4,4,6-

trimethyldihydropyrirnidine 114949 252-(3,4,4-trifiuoro-3-butenylthio)-benzoxazole 1 5385 (2. 5)2-(3,4,l-triflllOIO-Ii-blltGIlYltlil0)-bGI1Z0thla- Zole 1. 5863 (2. 5)2-(3,4,4-1;rifiuoro-3-butenylthio) -4- methylthiazole 1. 5358 (1)Bis(3,4,4-trifluoro-3-butenyl) ethylenebis(ditliioearbamate) 1. 5292Phenyl 3,4,4-trifiuoro-3-butenyl sulfide 1 5442 503-phenyl-5-(3,4,4-trifiuoro-3-buteny1thia) 1,2,4-thiadiazo1e 1. 5687 (2.5) 3,4,4-tri1'iuoro-3-butenyl beuzyl sulfide. 1. 5120 253,4,4-trifiuoro-3-butenyl-a-naphthyl sulfid 1. 5805 (50)N-(3,4,4-trifiuoro-3butenyl)phthalimide. (2. 5) Bis(3,4,4-trifiuoro-3-butenyl) disulfide (2. 5)2-(3,4,4-trifluoro3-butenylthio) -pyridine 1. 5258 254-(3,4,4trifluoro-3-buteny1thio)-pyridine 1. 5471 (2. 5)N-(3,4,4-trifluoro-3-butenyl) 2,4-

thiazolidenedione 1. 4678 l S em isolid 2 Liquid.

NorE.-Figure in parentheses are partial control.

The compounds of the present invention may be used as effectivenematocides and may be applied in a variety of ways at variousconcentrations. In practice the compounds are usually formulated with aninert nematocidal adjuvant, utilizing methods well-known to thoseskilled in the art, thereby making them suitable for application asdusts, sprays, or drenches. The amount applied will depend upon thenature of the nematode to be controlled and the rate of application mayvary from 1 to pounds per acre. One particularly advantageous Way ofapplying the nematocidal composition comprising the adjuvant and aneffective amount of a compound of the present invention is as a spray,drench or dust followed by incorporation.

Various changes and modifications may be made without departing from thespirit and scope of the invention described herein as will be apparentto those skilled in the art to which it pertains.

I claim:

1. The compound,3-phenyl-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-thiadiazole.

References Cited UNITED STATES PATENTS 3,223,707 12/1965 Brokke 260251ALEX MAZEL, Primary Examiner R. J. GALLAGHER, Assistant Examiner US. Cl.X.R.

